The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries...The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds o...Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.展开更多
Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to b...Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on Co O(111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy.At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ)experiences surface electron rearrangement from IS(intermediate-spin state) to LS(low-spin state) and then returns to IS/HS(high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.展开更多
基金supported by the financial support from the Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120095)the National Natural Science Foundation of China(Nos.52471229 and 52171210)the Jilin Province Science and Technology Department Program(No.20240101004JJ).
文摘The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.YDZJ202201ZYTS313,YDZJ202201ZYTS395,20240402072GH,and 20240101004JJ)the National Natural Science Foundation of China(Nos.22201097 and 52171210)。
文摘Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.
基金financially supported by the National Natural Science Foundation of China(No.52171210)the Program for the Development of Science and Technology of Jilin Province(Nos.20240101004JC,20220201130GX,and 20240402072GH)。
文摘Oxygen evolution reaction(OER) is one of the most important half-reactions related to metal-air batteries,fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on Co O(111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy.At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ)experiences surface electron rearrangement from IS(intermediate-spin state) to LS(low-spin state) and then returns to IS/HS(high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.
